POLYMERS

“the greatest joy of my life”

The term "polymer" was coined in 1833 by Jöns

Jakob Berzelius
Polymers were considered by
Hermann Staudinger as macromolecules
ANCIENT POLYMERS

 Naturally occurring polymers (those derived from plants

and animals) have been used for centuries.
 Wood – Rubber
 Cotton
 Silk

 Oldest known uses

 Rubber balls used by Incas
RUBBER TREE

Cotton
VULCANIZATION
POLYMERS IN Starch
BIOLOGY

DNA

Protein
 Terminology
Monomers or building blocks ( a mol. must have
bonding sites or functional groups).
Polymers (e.g. polyethylene, polymethylmethacrylate,
PVC)
Polymerization

Degree of polymerization (DP) : number of repeating

units present.
n H2C CH2 * CH2 CH2 *
n
Functionality
( no. of binding sites/ functional
groups present)

Tacticity:
Classification of polymers

On the basis of occurrence:

Natural Polymers: wool, silk, protein, wood, cellulose, jute,
cotton, natural rubber, etc.
Synthetic Polymers: PE, PVC, resin, etc.

On the basis of thermal behaviour:

Thermoplastic: PE, PMMA etc.

Thermosetting: bakelite, epoxy resin, etc.

On the basis of types of polymerization:

Addition polymerization: PE, PVC, PMMA, etc.
Condensation polymerization: bakelite, nylon-6,6
On the basis of chemical structure:
Linear polymers: HDPE, all thermo plastics.
Branched polymers: LDPE, polystyrene, PMMA.
Cross linked polymers: bakelite, urea-formaldehyde.
On the basis of presence of organic or inorganic group:
Organic Polymers: PE, PVC, PMMA, PTFE, PC, etc.
Inorganic polymers: Silicon, polyboron nitrides etc.

On the basis of streochemistry:

Atactic:
Isotactic:
Syndiotactic:
On the basis of end use:
Elastomer: natural rubber, buna-S, silicon rubber
Fiber: jute, silk, nylon etc.
Resin: urea-formaldehyde
Plastic: PE, PVC, Teflon, etc.

On the basis of monomers:

Homopolymers: PE,
Copolymers:Styrene-Butadine,
acrylonitrile-butadine-styrene etc.
Types of Polymerization
Addition (chain Growth) Polymerization:

• Addition of monomers
• No byproduct is formed
• usually in presence of free radical initiator

n H2C CH2 * CH2 CH2 *

n
Main features:
• vinyl compounds undergo this polymerization
• Double bond provide required bonding sites
• Rapid addition of monomer takes place
• Elemental composition remains same for both reactants and product
Condensation (Step Growth) Polymerization:

• Bi-functional/Polyfunctional monomer
• Intermolecular condensation
• Continuous elimination of byproduct
• usually in presence of free radical initiator

n HOOC-(CH2)4-COOH
adipic acid
+ [-OC-( C H2)4-CO-NH-(CH2)6-NH-]n + 2n H2O
n H2N-(CH2)6-NH2 Nylon 6,6
hexammethylene diamine
Main features:
• Polymerization is catalyzed by acids/alkalis
• Polymerization is slow & stepwise
• Elemental composition is different for both reactants and product
 Polymer

Polymer: High molecular weight molecule made up of a small

repeat unit (monomer).
A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A

Oligomer: Short polymer chain

Copolymer: polymer made up of 2 or more monomers

Random copolymer: A-B-B-A-A-B-A-B-A-B-B-B-A-A-B
Alternating copolymer: A-B-A-B-A-B-A-B-A-B-A-B-A-B
Block copolymer: A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B
Structure-Property Relationship of Polymers

Structure depends upon

 Size of polymer chain
 Shape of polymer chain
 Chemical nature of the monomer

Effect of Structure
 Physical & Chemical property

 Strength
Melt viscosity, impact & tensile strength

Tensile strength & impact strength α

molecular mass
* Polymer is commercially useful if have
high tensile strength and low flow/melt
viscosity
 Crystallinity

*Polymer have crystalline and amorphous parts

*Degree of crystallinity of the polymer depends upon its
structure, linear polymer have high crystallinity. (HDPE is
more crystalline than LDPE which is more as compared to
polystyrene).
* Polymer chain having polar group have high crystallinity.
* Isotactic & Syndiotactic polystyrene is highly crystalline.

 Elasticity

* Uncoiling & recoiling on application of force

* Breaking can be avoided by: cross linking, avoiding
bulky groups etc.
* Polymer chain having polar group have high
crystallinity.
CRYSTALLINITY
 Non-Elastic Nature

* Due to crystallizablity
* Chain mobility is reduced due to cross linking
•Polar group & aromatic/cyclic groupimpart strength
(e.g Nylon 6,6)

 Plastic deformation

* Studied with application of temp. & pressure

*Thermoplastic deformation (Plastic deformation), due to linear structure
* Thermosetting polymer : no deformation

 Chemical resistivity

* Depends upon structure of polymer and nature of attacking reagent

*Depends upon presence of polar/non-polar group, molar mass, degree of
crystallinity
* Higher molecular mass less is dissolution
* Increase crystallinity increases chemical resistivity
 Glass Transition Temperature (Tg)
* Temperature below which a polymer is hard, brittle (glassy) and above which it is
soft, flexible (rubbery)

* Glassy State: No segmental or molecular movement

•Rubbery State: segmental motion but no molecular movement
 Factor Effecting Tg:

Flexibility: Linear chain (C-C, C-O, C-N) provide freedom to roation, large
group hinder the rotation, thus inc. Tg
e.g. polyethylene = -110
Side Group: e.g: poly α- methyl styrene ( 170) / polystyrene (100 ) extra methyl
gr. restrict rotation
Intermolecular forces: Polar gr. Inc. intermolecular forces, restrict
segmental/molecular mobility, inc. Tg
e.g. polypropylene (- 18) , Nylon 6,6 ( 57)
Branching & cross linking: small branching reduce Tg & vice-versa
e.g. LDPE lower Tg value than XLDPE
Plasticizer: Reduce
Stereo-regularity: inc. with inc. in Stereo-regularity e.g. Isotactic polymer has
higher Tg than atactic
Molecular weight: Tg inc. with inc. in molecular
weight
Significance of Tg:

* Flexibility measure

* Idea of thermal expansion, heat capacity, RI, electrical & mechanical

properties
* Tells about the nature of polymer
* Tg & Tm Provides the knowledge about fabrication of material
 Thermoplastic Polymer

Formed by addition polymerization

Long-chains
Undergo reversible changes on heating
Polymers of low molecular weight
Soft, weak and less brittle
Soluble in organic solvents
Soften, reshaped and reused on heating
No change in chemical composition during molding process.

Thermosetting Polymer

Formed by condensation polymerization

Three dimensional network structure
Undergo irreversible changes on heating
High mol. Weight
Hard, strong and more brittle
Insoluble in organic solvents
Do not soften and reshaped on heating
Change in chemical composition.
Classification of Plastics:
Thermoplastic Thermosetting

Formed by addition Formed by condensation

Linear chain with negligible cross-link 3D network, covalent bonding
Reversible change on heating Irreversible change on heating, degrade
Soften on heating Doesn’t soften on heating
Soft, weak & less brittle Hard, strong & more brittle
Soluble in org. solvents Insoluble in org. solvent
Low molecular weight High molecular weight
Reshaped & reused Can’t be reshaped & reused
No change in chemical composition Change in composition while molding

PE, PVC, PTFE Bakelite

Commercial thermoplastics
Polyethene (PE)

 Generally Homopolymer of ethene/ethylene

 Addition polymerization
 LDPE & HDPE are homopolymers

LDPE (Low Density PE)

Applications
 Transparent film
 Squeeze bottle
 Paper coating
 wrapping
 table clothes
 Container & sheets
 Cable wire & insulation
 HDPE (High Density PE)

 Linear polymer with little or no branching

 Low pressure required, low temp (< 100 0C)
 Ziegler-Natta catalyst (Al(C2H5)3 TiCl4) used

Applications
 Dustbin
 Milk bottle
 cans
 drums
 containers
 fuel tanks
 pipes
 cable insulation
PP (Polypropylene)
 Linear polymer
 Low pressure required
 Ziegler-Natta catalyst (Al(C2H5)3 TiCl4) used
 (90% or more of the polymer is isotactic form
 monomer are added in head to tail fashion

Applications
 Fiber
 appliance components
 Packaging containers
 furniture
 Toys
 Pressure sensitive tape
 POLYPROPYLENE

Application:-
For making packaging container, furniture and toys.
 PS (Polystyrene)

 Bulk/Suspension polymerization of styrene

 Free radical polymerization

Applications
 combs, toys
 Radio, TV parts
 Video cassettes
 refrigerator parts
 electric insulation material
 Thermacol
 PVC (Polyvinyl Chloride)

 Free radical polymerization

 80 % polymerization is suspension else is
emulsion polymerization
 Needs 50-75 oC
 Most versatile due to its blending ability with
plasticizers

Applications
 building & construction
 pipes, flooring & vinyl siding
 wire, cable insulation
 Packaging
 Flexible films
 artificial leather, wall covering
Polystyrene (PS)

Used in making video cassettes,

radio and television parts.

Polyvinylchloride (PVC)

Used in making cable insulator,

Rigid pipes etc.
PTFE (Polytetrafluoroethylene)/TEFLON

 Linear polymer
 Emulsion polymerization , peroxide initiator

Applications
 Insulation of motor, generator, wires, cable
 Coating in food processing units
 anti corrosive coat in weapons
 industrial filters, belts
 Cardiovascular grafts, heart patches
 Ligament of knees
Polytetrafluoroethylene/Teflon (TFE)

Used for insulation of coil, capacitor, wires.

 Some Important Synthetic and Semi-synthetic Fibers

Nylons (polyamides) are polyamide.

Adipic acid

Nylon-6,6

Application: Making sports gear, fishing lines, sports equipments

Making brushes and combs.